Conductivity, electronic polyethylene

A further approach to electrically wire redox enzymes by means of supramolecular structures that include CNTs as conductive elements involved the wrapping of CNTs with water-soluble polymers, for example, polyethylene imine or polyacrylic acid.54 The polymer coating enhanced the solubility of the CNTs in aqueous media, and facilitated the covalent linkage of the enzymes to the functionalized CNTs (Fig. 12.9c). The polyethylene imine-coated CNTs were covalently modified with electroactive ferrocene units, and the enzyme glucose oxidase (GOx) was covalently linked to the polymer coating. The ferrocene relay units were electrically contacted with the electrode by means of the CNTs, and the oxidized relay mediated the electron transfer from the enzyme-active center to the electrode, a process that activated the bioelectrocatalytic functions of GOx. Similar results were observed upon tethering the ferrocene units to polyacrylic acid-coated CNTs, and the covalent attachment of GOx to the modifying polymer. 

Although the motion of protons does not lead to electrical conduction in the case of benzoic acid, electronic and even ionic conductivity can be found in other molecular crystals. A well-studied example of ionic conduction is a film of polyethylene oxide (PEO) which forms complex structures if one adds alkaline halides (AX). Its ionic conductivity compares with that of normal inorganic ionic conductors (log [cr (Q cm)] -2.5). Other polymers with EO-units show a similar behavior when they are doped with salts. Lithium batteries have been built with this type of... 

Polyacetylene retains multiple bonds along the chain. Electrons can be conducted through the series of tt-orbitals. A resonance form of the Lewis structure can be drawn, showing that the electrons may be delocalized along the polyacetylene chain. No such resonance form is possible for polyethylene. 

Johnson and Willson interpreted the main feature of the observations on solid polyethylene doped with aromatic solutes in terms of an ionic mechanism it was analogous to that proposed for irradiated frozen glassy-alkane-systems in which ionization occurred with G = 3 — 4 [96], The produced charged species, electron and positive hole, were both mobile as indicated by the radiation-induced conductivity. The production of excited states of aromatic solutes was caused mainly by ion-electron neutralization. The ion-ion recombination was relatively slow but it might contribute to the delayed fluorescence observed. On the basis of Debye-Simoluchovski equation, they evaluated the diffusion coefficients of the radical anion of naphthalene and pyrene as approximately 4 x 10 12 and 1 x 10 12 m2 s 1 respectively the values were about three orders of magnitude less than those found in typical liquid systems. 

Figure 4. Backbone structures of salt-solvating polymers. The figure shows the similarity of backbone structure, with optimal spacing between electron-donating oxygens, of polymers that form ion-conducting salt complexes. PPL-poly-3-propiolac-tone PEO polyethylene oxide PPO 1,2- polypropylene oxide.18...

The simplest polymer with a conjugated backbone is polyacetylene. Its structure is similar to that of the saturated polymer polyethylene, but has one of the hydrogen atoms removed from each carbon of the polyethylene chain. Each carbon atom in the polyacetylene chain thus has one excess electron which is not involved in the basic chemical binding. And if the separation of the carbon were constant, polyacetylene would conduct along the chain in other words it would behave like a metal in one dimension. But unfortunately this is not true as the free electrons tend to get localized in shorter double bonds. Conjugated polymers can at best be expected to display semiconducting properties. 

Silver oxide cells were developed in the 1960s. These cells use silver oxide mixed with carbon (to increase the electronic conductivity of the material) as cathode, amalgamated pellet zinc powder as anode, and a solution of potassium hydroxide or sodium hydroxide with dissolved zin-cates in water as electrolyte. Permion (a radiation graft of methacrylic acid onto a polyethylene membrane) is used as separator. The cell reactions are... 

In the usual space-charge limited theory, electrons are injected into the insulator conduction band, and some of these electrons are immobilized in localized defect states. We have considered an alternate mechanism more appropriate to the polymer structure. Contact charge transfer studies in Polyethylene Terephthalate (PET) and other polymers (15-16) suggest that the electronic states accessible from metal contacts are localized molecular-ion states located deep in the forbidden energy gap. Charge transport is by hopping between localized states. 

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